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Issue 9, 2011
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Syntheses and structures of the first terminal phosphanylphosphido complex of hafnium [Cp2Hf(Cl){η1-(Me3Si)P–P(NEt2)2}] and the first zirconocene-phosphanylphosphinidene dimer [Cp2Zr{μ2-P–P(NEt2)2}2ZrCp2]

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Abstract

Reactions of (Et2N)2P–P(SiMe3)Li with [Cp2MCl2] (M = Zr, Hf) in toluene or pentane yield the related terminal phosphanylphosphido complexes [Cp2M(Cl){η1-(Me3Si)P–P(NEt2)2}]. The solid state structure of [Cp2Hf(Cl){η1-(Me3Si)P–P(NEt2)2}] was established by single crystal X-ray diffraction. The reaction of (Et2N)2P–P(SiMe3)Li with [Cp2ZrCl2] in THF or DME solutions leads to the formation of deep red crystals of the first neutral diamagnetic zirconocene-phosphanylphosphinidene dimer [Cp2Zr{μ2-P–P(NEt2)2}2ZrCp2]. The molecular structure of this compound was confirmed by X-ray diffraction. The reactions of (R2N)2P–P(SiMe3)Li with [CpZrCl3] yield the related tetraphosphetanes R2NP(μ2-PSiMe3)2PNR2, which apparently are formed as a result of a transfer of NR2 groups from a P atom to the Zr atom.

Graphical abstract: Syntheses and structures of the first terminal phosphanylphosphido complex of hafnium [Cp2Hf(Cl){η1-(Me3Si)P–P(NEt2)2}] and the first zirconocene-phosphanylphosphinidene dimer [Cp2Zr{μ2-P–P(NEt2)2}2ZrCp2]

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Publication details

The article was received on 18 Aug 2010, accepted on 08 Dec 2010 and first published on 31 Jan 2011


Article type: Paper
DOI: 10.1039/C0DT01040E
Citation: Dalton Trans., 2011,40, 2017-2024
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    Syntheses and structures of the first terminal phosphanylphosphido complex of hafnium [Cp2Hf(Cl){η1-(Me3Si)P–P(NEt2)2}] and the first zirconocene-phosphanylphosphinidene dimer [Cp2Zr{μ2-P–P(NEt2)2}2ZrCp2]

    R. Grubba, A. Wiśniewska, K. Baranowska, E. Matern and J. Pikies, Dalton Trans., 2011, 40, 2017
    DOI: 10.1039/C0DT01040E

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